Organic Reactions Summary Alkenes, Alkynes and Variations For Use As A Study Guide Beauchamp

Alkenes, Alkynes & Variations Beauchamp 1
Organic Reactions Summary

Alkenes, alkynes and variations
For Use as a Study Guide
Beauchamp
y:\files\classes\Organic Chemistry Tool Chest\Reactions Lists\Org rxns summary, alkenes, -ynes, with mechs.doc
Making alkenes and alkynes
a. mechanism using potassium t-butoxide, KOC(CH3)3, SN2 at and E2 at 1o, 2o and 3o RBr,
H3 C H SN2 H3C H
O
C C Br O C
H3C Br
H H
CH3 H H
D H H
E2 D
C Br C C D
H3C
O H R Z
CH3 C C E Br
C Ha C Hb H3C
H3C CH3 Ha
CH3 Hb
H
H3C
O C Br
C H C E2 (-CH2-H)
H3C H2 E2 Br
CH3 CH3
Ha C E2 (-CHb-H)
Hb E2 (-CHa-H)
Example reactions
E2 > SN2
KOC(CH3)3 anti
Br elimination
Br
KOC(CH3)3 E2
KOC(CH3)3 E2
Br
R Br
KOC(CH3)3 E2
S S
H3C
CH3
Br C
KOC(CH3)3 O CH3 S N2
no other
option
b. Double elimination from dibromoalkanes to form alkynes and terminal acetylides used in many additional
reactions (SN2 with RBr, C=O addition to aldehyses and ketones, and reaction with epoxides)
Br Br Br
2 eqs. Br2 H
h Na
H Na
N N
H R R N R R
H
R R 3rd equivalent
H most stable
a anion in mixture
O
H a H H Na
2. workup
H2 b
2.
H2 C
b Na
C X R
R
H
O SN2
c
O H c
CH H2O H 2.
b R CH C Na
R O R
b d d
HO 2.
H2O H O Na
O
The zipper reaction moves a triple bond in an unbranched linear chain to the end and allows all of the above
reactions.
H2
C CH2 CH2
C H Na C
N C
C R R C C
R R R
H
N
R R
R R
N H
H H
Na H C C
C C
C C
R R C H
C C C R
R C
C H
H H Na
H H N H
N
R R R R
R R
N
H
C
2. workup
C H H
R
C C
O
H H C
H H R
C
H2
c. mechanism using NaCC-R to make a bigger alkyne, SN2 at methyl, 1o and 2o RBr and only E2 at 3o RBr,
H H
SN2
C C Br R C C C
C Br
H
R H
H H
D D
SN2
C C Br R C C C Br
C H R
H
R CH2 H2C
H3C CH3
H
H3C H
C C Br
C H C Br
E2 > SN2 O C
R H2
CH3 H
Ha C E2 (-CH2-H) E2 (-CHa-H) H2C
E2 (-CHb-H) CH3
SN2
Hb
Example reactions
SN2
NaCC-R inversion of
Br configuration
R
Br
NaCC-R
R E2 > SN2
NaCC-R E2
Br
R Br
NaCC-R E2 > SN2
S S
C achiral
Br NaCC-R C
R SN2
d. mechanism using triphenylphosphine to make triphenylphosphonium salt, SN2 at methyl, 1o and 2o RBr and
only E2 at 3o RBr, used to make a triphenylphosphonium ylid to make Z and E alkenes with aldehydes and ketones.
Br
Ph H Ph
Br Ph H O
SN2 Ph
Ph P C CH2 1. n-BuLi CH3
Ph P C 2. H2C=O P C
Ph H CH3 CH3 Li Ph C H CH3
Ph H H
ylid salt betaine
Ph = phenyl
H Ph O Ph O
Ph Ph Ph
C H H
H CH3 P C P C
Ph P O C Ph C CH3 CH3
Ph C
Ph Z alkenes
CH3 H CH3 H CH3
oxaphosphatane
Br H3 C
Ph H Ph O
Br Ph H
SN2 Ph
Ph P C CH2 1. n-BuLi CH2
P C P C
Ph 2. H2C=O
Ph C H CH3
Ph H3C CH2 CH2 Li
Ph CH3 CH3
H3 C ylid salt CH3 betaine
Ph = phenyl
H Ph O Ph O
Ph Ph Ph
C H H
H3C CH3 P C P C
Ph P O C Ph C CH3 CH3
Ph C
Ph Z alkenes
CH2 H3C CH2 H3C CH
2
H3C H3 C oxaphosphatane H3 C
Schlosser Modification of the Wittig reaction to make E alkenes
H OH2
H
H H H
O C
O C Ph3P O C O C
Ph3P acid/base Ph3P
R Ph3P
C H at -78oC R neutralize
R C R
C H C R
R The stereochemistry
R R H
betaine H2C of the alkene is
flat sp2 carbon determined in this step.
Li
can react from
extra equivalent of n-BuLi
either side
H H
O O C
Ph3P C R Ph3P
R C R
phosphine C R
oxide
H H
E alkene
Example reactions
1. Br
P
2. n-BuLi
Ph Ph Normal Wittig
3. CH3CH=O
Ph Z alkene preferred
1. Br
P R
Ph Ph 2. n-BuLi
Ph 3. CH3CH=O Normal Wittig
Z alkene preferred
1.
P Br
Ph Ph 2. n-BuLi
Ph 3. CH3CH=O E2
1. R Br
P
S
Ph Ph 2. n-BuLi
Ph 3. CH3CH=O Normal Wittig
S Z alkene preferred
1.
Br
P
Ph Ph
Ph 2. n-BuLi Normal Wittig
3. CH3CH=O Z alkene preferred
1. Br
2. n-BuLi
P 3. CH3CH=O
4. -78oC, n-BuLi Schlosser modification
Ph Ph of the Wittig
Ph 5. HCl, warm
E alkenes preferred
e. Ohira-Bestmann modification of the Seyferth-Gilbert reaction (makes terminal alkynes from aldehydes and a
special ‘Wittig’ reagent). Overall reaction from aldehyde to the terminal alkyne – simplified Ohira-Bestmann
reaction
O O
O O H O O
P K
R
OMe K N R P
R H OMe R N O O OMe
N OMe
given terminal
N alkynes
Possible mechanism – with mechanism details
O O O
O O
O
O P P
R P
R OMe O OMe R OMe
OMe OMe O OMe
N N N
N given O
N N
R H R H R H
H C C
C O O
O O
C C C
R O R P
R P
N N OMe
resonance OMe H OMe
O P H OMe
N N OMe N
N N
rearrangement = N2 leaves, OMe
N N
and H migrates across N
Example reactions
1. RO Na
O O O
P 2.
OMe H difficult to make
OMe alkyne at branch
N2 point
1. RO Na
O O
2. O
P
OMe difficult to make
OMe H alkyne at branch
N2 point
1. RO Na
O O O
2.
P
OMe H difficult to make
OMe alkyne at branch
N2 point
f. ROH with sulfuric acid / heat. Synthesis of alkenes (our only useful E1 reaction. Rearrangement is
possible).
H H
H O SO3H
O SO3H
H O H O H
H

(heat) H
O O E1
H H O SO3H H
slow step
H O SO3H
pKa = -10 water is a good H
secondary alcohol leaving group bp = +83oC
bp = +161oC alcohol alkene distills out
Tbp = 78oC
H  H H O
H CH3
O (heat) H H CH3
O H H
H O SO3H H3C C H3C C
C C C C
H rearrangement H
pKa = -5 slow step CH3 H H
CH3
alcohol 2o carbocation 3o carbocation
H3C
H
H3 C C
HO3S O H O H C CH3
alkene
(E1 mechanism) CH3
Example reactions
OH H2SO4 /  probably E2
OH
H2SO4 / 
E1
H2SO4 / 
E1
OH
OH
H2SO4 /  E1
OH
E1
H2SO4 / 
rearrangement
g. Making Allylic Alcohols from Epoxides using LDA (E2 reaction using LDA + epoxides)
a
H
O Li H
Li O
O O
C C H
H H N H H H
C C
H CH2 H C C
E2-like H CH2 2. workup
H
reaction H CH2
H
proton
LDA, lithium diisopropyl amide transfer
(always a base in our course)
b
H
O Li H
Li O
O O
C C CH3
H CH3 N H H CH3
C C
H C  H2 H C C
E2-like H C  H2 H
2. workup H C  H2
H reaction
proton
LDA, lithium diisopropyl amide transfer
(always a base in our course)
Example reactions
OH
1. LDA, -78oC
O 2. workup
allylic alcohols,
can oxidize to C=O
O
1. LDA, -78oC OH
2. workup
allylic alcohols,
can oxidize to C=O
allylic alcohols,
can oxidize to C=O
O 1. LDA, -78oC OH
2. workup
Reactions of alkenes, alkynes and conjugated variations

a. RBr from alkenes (anti-Markovnikov addition of HBr using free radical chemistry):
mechanism using HBr / ROOR / h for free radical addition to alkane pi bonds (anti-Markovnikov addition = Br
adds to less substituted position to form most stable free radical intermediate, and then H adds to more substituted
position)
HBr H2
overall reaction H C Br
C R2O2 (cat.)
h H3C C
H3C CH2 H2
1. initiation (two steps)

R O
h R O H = 40 kcal/mole
O R
O R
(cat.)
R BE = +88 kcal/mole
R H Br BE = -111 kcal/mole
O H Br
O H = -23 kcal/mole
reagent
2a propagation
H H
C BE = +63 kcal/mole
H3C CH2 Br BE = -68 kcal/mole
C Br
H3C C H = -5 kcal/mole
H2
2b propagation H
H2 BE = +88 kcal/mole H = -15
C Br C Br BE = -98 kcal/mole
H Br Br
H3C C H3C C both steps
H2 H2 H = -10 kcal/mole (2a + 2b)
3. termination = combination of two free radicals - relatively rare because free radicals are at low concentrations
H H Br
Br
C Br C Br H = -68 kcal/mole
H3C C H 3C C
H2 H2
CH3
H H H2
C CH Br H = -80 kcal/mole
Br C C Br
Br CH C
C CH3 H3C C H2
H2 H2
CH3 very minor products
Example reactions
H-Br / h
ROOR (cat.) Br achiral
Br2 / h
ROOR (cat.)
Br achiral
Br
Br2 / h
ROOR (cat.) R/S
enantiomers
Br
Br2 / h
ROOR (cat.) cis and trans
b. RBr from alkenes (anti-Markovnikov addition of HBr using borane chemistry):

--
mechanism using 1. BH3 2. Br2 / CH3O for anti-Markovnikov addition of H-Br to alkane pi bonds (concerted, syn
addition of H-BH2 to alkene pi bond, followed by complex with Br2 and migration of R group to Br)
H2
overall reaction H 1. (BH3)2 C Br
C
2. Br2, CH3O H3C C
H3C CH2 H2
step 1 R
CH3 H3C H
H
B R B R
C C
H2C CH H2C C H
R
syn addition, with
H2C CH2 H at more substituted H2C CH2
C position and B at less C
H2 substituted position. H2
step 2
R
R R
H 3C H H3C H H3C H
B R
B R B R
C C C
H Br Br Br Br Br
H 2C C H2C C H2C C
H H
H 2C CH2 H2C CH2 H2C CH2 Br
C C C
H2 H2 H2
H3C O
R R
H3C H
R H3C H R
B B
C CH3 CH3
Br O C O
H2C C Br
H2C C
H
H2C CH2 H
H2C CH2
C
H2 C
H2
Example reactions
1. (BH3)2 Br
2. Br2, CH3O achiral
1. (BH3)2
2. Br2, CH3O Br achiral
Br
1. (BH3)2
2. Br2, CH3O R/S
enantiomers
1. (BH3)2 Br
2. Br2, CH3O
() or (dl) enantiomers
c. Alkenes with aqueous sulfuric acid. Alcohol synthesis (Markovnikov addition, rearrangements are
possible).
Attack
Protonate H carbocation Acid/base
H with water H H
alkene proton
pi bond. H nucleophile. transfer.
C H3C C CH3
H O H H3C C CH3
slow step H3C C
H O H
H O
alkene O
H H H H
H O H alcohol
H H H H
H
H H
H O H H3 C C H3C C
slow step C C C C
H rearrangement H
alkene CH3 H CH3 H
2o carbocation H O H 3o carbocation
CH3
CH3
CH3 H3C C CH2
acid catalysis CH3
alkene + water alcohol
H3 C C C O
H2
alkene + alcohol acid catalysis H3C H
ether O
H alcohol H O
Example Reactions
OH
H2SO4 / H2O hydration
(H3O+)
achiral
OH hydration
H2SO4 / H2O
(H3O+) enantiomers
(R and S)
OH hydration
H2SO4 / H2O
(H3O+) enantiomers
(R and S)
OH
hydration
H2SO4 / H2O
(H3O+)
achiral
OH hydration
H2SO4 / H2O
(H3O+)
achiral
rearrangement
hydration
H2SO4 / H2O
(H3O+)
OH diastereomers
S S (SR and SS)
d. Alkenes with alcohol + sulfuric acid. Markovnikov addition, ether synthesis (rearrangements are possible).
H H
H H
H
C H3C C CH3
H O CH3 H3C C CH3
slow step H3C C
H O CH3
H O
alkene O
H H3C H H3C
H O CH3 ether
H H H H
H CH3
H H CH3
H O CH3 H3C C H3C C
slow step C C rearrangement C C H3C C CH2
H H
CH3 H CH3 H O
alkene
2o carbocation H O CH3 H3C H
3o carbocation H3C O
acid catalysis H
alkene + water alcohol
CH3
CH3
alkene + alcohol acid catalysis
ether H3C C C
H2
O
H3C ether
Example Reactions
OR hydration
H2SO4 / ROH
(ROH2+)
achiral
OR hydration
H2SO4 / ROH
(ROH2+) enantiomers
(R and S)
OR hydration
H2SO4 / ROH
(ROH2+) enantiomers
(R and S)
OR
H2SO4 / ROH hydration
(ROH2+)
achiral
O
R hydration
H2SO4 / ROH
(ROH2+) achiral
rearrangement
hydration
H2SO4 / ROH
(ROH2+) OR
S diastereomers
S (SR and SS)
e. Alkenes with 1. HgX2 / H2O 2. NaBH4. Alcohol synthesis with minimal rearrangements (Markovnikov).
mercuric acetate
Hg(OAc)2
O O
O O
O Hg O
O Hg O
+
These d orbital electrons on mercury are available. They ethanoate has a Hg(OAc)
are not usually drawn, but are helpful for understanding common name of electrophile
the Hg+ bridge in the cationic intermediate. acetate = OAc
H
H
O
O O  O
resonance
Hg O Hg O Hg O
The large mercury atom with extra d electron densitiy bridges

across the two carbons (like Br+ in the next section) or the protonated
epoxide bridge and prevents rearrangement. Nucleophilic attack in the
H R = H = water nucleophile next step occurs from the opposite side to the mercury bridge and
H
forms alcohol product occurs at the more + carbon (the more substituted carbon). H
O
R O R = C = alcohol nucleophile H H H
H
forms ether product O H
O O
proton
H transfer
The initial adduct is a stable, organomercury compound, O O

but is not usually isolated. It is relatively toxic and need
not be isolated. The next step can be run in the same Hg O Hg O
reaction pot (reduction of mercury with NaBH4).
H O The Hg bridge helps to

prevent rearrangement.
O O
H H B H H
H O O
O
H
Hg O
O H
H Hg Hg
H H H H H
H B
H
Hg metal
H
SN2 nucleophilic attack by hydride at the mercury Free radical dissociation of A hydrogen atom is abstracted from the
atom displaces acetate as the leaving group. the weak Hg-C bond occurs. mercury by the highly reactive carbon free
Acetate can complex at boron taking the place of Other free radical reactions
are possible here, but not radical. This forms mercury metal as one of
the transferred hydride. This keeps boron with an emphasized in our course. the products. No stereoselectivity is observed
octet, which also is negatively charged. here because of the sp2 free radical carbon.
Example Reactions
OH
1. HgX2 / H2O
2. NaBH4 achiral
OH
1. HgX2 / H2O enantiomers

2. NaBH4 R and S
OH
1. HgX2 / H2O
2. NaBH4 enantiomers
R and S
1. HgX2 / H2O
2. NaBH4 achiral
OH
OH
1. HgX2 / H2O
2. NaBH4 achiral
no rearrangement
1. HgX2 / H2O diastereomers

2. NaBH4 SR and SS
CH3
S S
OH
f. Alkenes with 1. HgX2 / ROH 2. NaBH4. Ether synthesis with minimal rearrangements (Markovnikov).
mercuric acetate
Hg(OAc)2
O O
O O
O Hg O
O Hg O
+
These d orbital electrons on mercury are available. They ethanoate has a Hg(OAc)
are not usually drawn, but are helpful for understanding common name of electrophile
the Hg+ bridge in the cationic intermediate. acetate = OAc
H
H3C
O
O O  O
resonance
Hg O Hg O Hg O
The large mercury atom with extra d electron densitiy bridges

across the two carbons (like Br+ in the next section) or the protonated
epoxide bridge and prevents rearrangement. Nucleophilic attack in the
H R = H = water nucleophile next step occurs from the opposite side to the mercury bridge and
H
forms alcohol product occurs at the more + carbon (the more substituted carbon). H3C
O
R O R = C = alcohol nucleophile H H3C H3C
H3C
forms ether product O H
O O
proton
H transfer
The initial adduct is a stable, organomercury compound, O O

but is not usually isolated. It is relatively toxic and need
not be isolated. The next step can be run in the same Hg O Hg O
reaction pot (reduction of mercury with NaBH4).
H3C O The Hg bridge helps to

prevent rearrangement.
O O
H3C H B H3C H3C
H O O
O
H
Hg O
O H
H Hg Hg
H H H H H
H B
H
Hg metal
H
SN2 nucleophilic attack by hydride at the mercury Free radical dissociation of A hydrogen atom is abstracted from the
atom displaces acetate as the leaving group. the weak Hg-C bond occurs. mercury by the highly reactive carbon free
Acetate can complex at boron taking the place of Other free radical reactions
are possible here, but not radical. This forms mercury metal as one of
the transferred hydride. This keeps boron with an emphasized in our course. the products. No stereoselectivity is observed
octet, which also is negatively charged. here because of the sp2 free radical carbon.
Example Reactions
O
1. HgX2 / CH3OH
2. NaBH4 achiral
O
1. HgX2 / CH3OH
enantiomers
2. NaBH4 R and S
1. HgX2 / CH3OH enantiomers

2. NaBH4 R and S
1. HgX2 / CH3OH
achiral
2. NaBH4
O
O
1. HgX2 / CH3OH achiral
2. NaBH4
no rearrangement
diastereomers
1. HgX2 / CH3OH SR and SS
2. NaBH4
CH3
S S
O
g. Electrophilic addition of HCl, HBr, HI to alkenes = Markovnikov addition, synthesis of RX compounds

with possibile rearrangements
H
H
Cl
C
Cl
a
H
a not this primary carbocation not observed
way (less stable)
b
H Cl
H Cl
Which carbon atom Cl
b C add a
reacts first, ...second? H2 nucleophile
tertiary carbocation only product
(more stable)
Forms pi bonds.
lose beta
proton
Starts
rearrange over.
There are two carbon choices for an electrophile to react with. Which carbon gives up the electrons and becomes
a carbocation is based on the most stable carbocation that can form (leading to a regioselective reaction). Such a
reaction is generally not stereoselective because the flat carbocation allows attack of the nucleophile to both
faces. We expect three possible reactions from the carbocation, add a nucleophile, lose a beta proton or rearrange.
c.
b achiral
Cl
rearrangement
H Cl
O b a Cl
O
OH a Cl 40%
(solvent) OH
achiral
40% Cl O O O
(dl mixture)
OH
resonance O O 20%
H
Example Reactions
Br
H-Br
only shows regioselectivity Markovnikov additioni

I I
D-I
D D
only shows stereoselectivity (dl) enantiomers
(dl) enantiomers
I I
D-I
D D
only shows stereoselectivity (dl) enantiomers
(dl) enantiomers
H-Br CH3 Br
Br CH3
shows regioselectivity but not stereoselectivity diastereomers (if no rearrangement)
H-Br
shows possible rearrangements Br
h. Electrophilic addition of HCl, HBr, HI to alkynes = Markovnikov addition, synthesis of RX compounds,

can use 1 equivalent or 2 equivalents
H
H CH2
C C
C H Cl C H
C
H3C H3C
H3C Cl
Cl
1 eq. HCl
CH2 CH3
CH3
Cl
C H Cl C Cl
C
H3C Cl H 3C
H3C Cl
2 eqs. HCl Cl
Br
H-Br
shows regioselectivity Markovnikov additioni
Br Br
H-Br
E/Z diastereomers
Br Br
H-Br Ph
Ph
shows regioselectivity E/Z diastereomers
H Cl
O
O
OH Cl
shows regioselectivity 50% / 50% O
(solvent)
i. Electrophilic addition of HCl, HBr, HI to conjugated diene or triene = Markovnikov addition, synthesis of
RX compounds, can use 1 equivalent or 2 equivalents
H +
A 1,2-addition 1,4-addition
C CH2
H3C C
H
H Br
C CH2
Br H H2C C resonance Br Br
H o
H Temp = -80 C 80% 20%
B
(a kinetic choice)
C CH2
H3C C Temp = +40oC 20% 80%
H (a thermodynamic choice when more energy is available)
a b
Br 3o carbocation Br
H is best
resonance
2 4
1 3
a
b
Br
Br
kinetic product thermodynamic product

larger + in intermediate more stable alkene
a b c
Br Br
H
resonance
4 6 resonance
2
3 5
1
a
H H b
Br H c
Br Br
1,2 addition - This looks second 1,4 addition 1,6 addition - This looks best
because the alkenes are conjugated. least favorable because because the alkenes are more
it breaks conjugation substituted and conjugated.
j. Alkenes with Br2 or Cl2. Synthesis of vicinal dihalide (anti addition).
Br
Br Br
CCl4 Br
85%
Br
Br
bromine is a red orange liquid (dl) mixture

dissolved in the solvent, the
color disappears as it is added
Cl
Cl
Cl CHCl3 Cl
81%
Cl Cl
meso (achiral)
chlorine is a green gas,

dissolved in the solvent
a Br Br
b
Br
Br HC CH2 CH2
Br HC HC CH
HC CH CH2 H2C H2C Br

CH2 a
HC Br
88% 12%
HC b
CH2 Br 1,4-addition is the 1,2-addition is the kinetic
CH2 thermodynamic product product because bromine
because the double bond attack is faster at the more
a
is more substituted (E or positive seconday carbon
Z is possible) atom.
Br bromination
Br Br
(or Cl2) Br enantiomers
R and S
Br
bromination
Br Br
(or Cl2)
meso, RS
Br
Br
Br Br bromination
Br
(or Cl2)
enantiomers
RR and SS
Br
Br Br bromination
(or Cl2)
enantiomers
Br RR and SS
bromination
Br Br Br
(or Cl2) Br
achiral
Br
bromination
Br Br
(or Cl2)
Br diastereomers
S SRR and SSS
Br
Br Br Br
3% 21%
Br
4
Br2 / CHCl3 / 0oC
2 3
Br Br Br
1 5% 71%
k. Alkenes with Br2/H2O or Cl2/H2O. Synthesis of bromohydrin or chlorohydrin (anti + Markovnikov

addition).
Br
Br Br Br H
H Br
O O
H H
H H
O
O H
O
Br H H
(dl) mixture
Cl
Cl H H Cl
Cl Cl O
O
H H H
H
O O H
O
H (dl) mixture H
Cl
OH anti + Markovnikov
Br2 / H2O addition
(or Cl2 / H2O) Br enantiomers
R and S
addition
Br2 / H2O
(or Cl2 / H2O)
enantiomers
RS and SR
Br
addition
Br2 / H2O Br
(or Cl2 / H2O) enantiomers
RR and SS
Br2 / H2O addition
(or Cl2 / H2O) enantiomers
RR and SS
Br
Br2 / H2O OH anti + Markovnikov

(or Cl2 / H2O) addition
Br achiral
no rearrangement
Br
Br2 / H2O anti + Markovnikov
(or Cl2 / H2O) addition
OH
S S diastereomers
SRR and SSS
l. Alkenes with Br2/ROH or Cl2/ROH. Synthesis of bromo or chloro “ethers”.
Br
Br Br Br H
H Br
O O
H CH3
H CH3
O
O H
O
Br H3C (dl) mixture H3 C
Cl
Cl H H Cl
Cl Cl O
O
H H CH3
CH3
O O H
O
H3C (dl) mixture H3 C

Cl
OR anti + Markovnikov
Br2 / ROH addition
(or Cl2 / ROH) Br enantiomers
R and S
OR
anti + Markovnikov
addition
Br2 / ROH
(or Cl2 / ROH)
enantiomers
RS and SR
Br
OR anti + Markovnikov
addition
Br2 / ROH Br
(or Cl2 / ROH)
enantiomers
RR and SS
OR
anti + Markovnikov
Br2 / ROH addition
(or Cl2 / ROH)
enantiomers
Br RR and SS
anti + Markovnikov
Br2 / ROH OR addition
(or Cl2 / ROH)
Br
achiral
Br
Br2 / ROH anti + Markovnikov
(or Cl2 / ROH) addition
OR diastereomers
S S SRR and SSS
m. Alkenes with 1. BH3 2. H2O2/HO--. Hydroboration/oxidation = anti-Markovnikov alcohols.

The mechanism for this reaction is given at the beginning of this document.
1. BH3 1. syn addition
2. H2O2 / HO OH 2. oxidation
achiral
OH 1. syn addition
1. BH3 2. oxidation
2. H2O2 / HO
enantiomers
R and S
OH
1. syn addition
1. BH3 2. oxidation
2. H2O2 / HO
enantiomers
R and S
1. syn addition
1. BH3 2. oxidation
2. H2O2 / HO
OH achiral

2. H2O2 / HO 2. oxidation
OH achiral
OH 1. syn addition
1. BH3 2. oxidation
2. H2O2 / HO
CH3 diastereomers
S S
SRR and SSS
H
n. Alkenes with 1. BH3 2. Br2/CH3O--. Hydroboration/bromination = anti-Markovnikov R-Br.

alkyl migration, with
CH2CH2R CH2CH2R bromide leaving R
RH2CH2C group, reacts 2x more
CH2CH2R
RH2CH2C B B but not shown. R B
3 Br Br CH2CH2R
CH2CH2R Br
Br
strong Lewis base Lewis acid Br trivalent
(trigonal planar) tetravalent H3C O boron
trivalent boron
boron Lewis
acid/base
reaction
Br Br R R
R
H2C R R B B Br
B(OCH3)4 H2 C R
C C CH3
H2 H2 O CH2CH2R
O
anti-Markovnikov product similar reactions,
3x total H3C tetravalent
A weaker -Br-Br bond is broken and a stronger (two more times)
C-Br bond is formed. Bromide is a good boron
leaving group in the strongly basic solution.

2. Br2 / CH3O Br 2. bromination
achiral
Br 1. syn addition
1. BH3 2. bromination
2. Br2 / CH3O
enantiomers
R and S

2. Br2 / CH3O 2. bromination
Br achiral
Br 1. syn addition
2. Br2 / CH3O
achiral
Br
1. syn addition
2. Br2 / CH3O
CH3
S diastereomers
S SRR and SSS
H
o. Alkynes with 1. HBR2 2. H2O2/HO--. Hydroboration/oxidation = anti-Markovnikov aldehydes.

Step 1
H
H
B O B O
H
H H H
reactive form of borane THF = tetrahydrofurane
borane/THF complex (a good Lewis acid)
R
R R
H H2C
H2C H2C
H B
H H H CH2
H CH2 CH2
H B R CH2 H B R CH2 H B
R H concerted
reaction C C
C C H C C H C C
C C
R H similar reaction R H similar reaction R H
H H H H a second time H H a third time H H
alkene + borane monoaklylborane diaklylborane triaklylborane
There are no more
hydrides to transfer.
The transfer of two electron pairs is concerted. The boron and hydrogen atom add from the same face (syn), so this reaction is
stereoselective. The boron adds at the less substituted carbon so this reaction is also regioselective. In subsequent reactions the
boron can be converted to another group in exactly the same position, so whereever the boron ends up will indicate the position of the
actual group introduced (OH or Br for us).
Step 2 H H
O O O H O O H O H
H
weak strong strong weak
There is a strong electron pair donor on each side of the equilibrium equation that
can complex with trivalenet boron, but only the peroxide anion reacts further. All
of these are present.
alkyl migration,
CH2CH2R with hydroxide CH2CH2R
H CH2CH2R RH2CH2C leaving group
CH2CH2R
O O RH2CH2C B B RH2CH2C B
CH2CH2R OCH2CH2R
O
strong Lewis base Lewis acid H O tetravalent trivalent
(trigonal planar) boron H O boron
trivalent
boron Lewis
acid/base
reaction
CH2CH2R
CH2CH2R
O CH2CH2R OCH2CH2R RH2CH2C
O RH2CH2CO OCH2CH2R
OCH2CH2R B
B
RH2CH2C O B
ligand O
trivalent O similar reactions,
H O dissociation
boron (two more times) H tetravalent
H
O H H boron
proton tetravalent
transfer boron
H2
C OH similar reactions,
H O R C (two more times)
H2 A weaker -O-O- bond is broken and a stronger C-O
bond is formed. Hydroxide, HO is an acceptable
Anti-Markovnikov alcohol is leaving group in the strongly basic solution
formed in a regioselective (compatible with the reaction conditions).
and stereoselective manner.
O anti-Markovnikov
1. HBR2 addition
2. H2O2 / HO
H aldehyde
O anti-Markovnikov
1. HBR2 addition
2. H2O2 / HO
aldehyde
H
O
1. HBR2
2. H2O2 / HO ketone
O O
1. HBR2
2. H2O2 / HO
2 ketones
p. Alkenes with CHCl3 / RO-- or CHBr3 / RO--. Carbene synthesis of dihalocyclopropanes.
Cl
Cl Cl
Cl
Cl C H O R Cl C Cl C = C
Cl Cl Cl Cl
chloroform alkoxide singlet carbene
(trichloromethane) strong base
pKa  25 A different type of elimination reaction.
Cl Cl
electron C electron
donation acceptance stereoselective reaction Cl Cl
concerted reaction C
R R (occurs in one step)
C C
C C R R
H H H H
"cis" alkenes form "cis" cyclopropane rings
"trans" alkenes form "trans" cyclopropane rings
q. Alkenes with CH2I2 / Zn (Simmons-Smith Rxn). Carbenoid synthesis of cyclopropanes.

Example Reactions
syn addition
CHBr3 / NaOH CBr2
enantiomers
R and S
CBr2
syn addition
CHBr3 / NaOH
enantiomers
RR and SS
CBr2 syn addition

CHBr3 / KOC(CH3)3
meso
RS and SR
syn addition
CHCl3 / NaOH CCl2
meso
RS and SR
CCl2 syn addition

CHCl3 / NaOH
achiral
syn addition
CHCl3 / KOC(CH3)3 CCl2
S S diastereomers
CH3 SSR and SRS
The first pair of dots represents

easily lost 4s electrons on zinc, Simmons-Smith reaction
I
that reduce a C-I bond.
I I Zn+2 Zn+2
I
I
H C I Zn H C H C
H H H carbenoid complex
The second pair of dots represents The stabilization by the metal makes the complex more
3d electrons on zinc that are stable, and less reactive. This makes the carbenoid
invoked in the metal complex. complex more selective for the desired reaction.
H H
electron C electron
donation acceptance H2
concerted reaction C
(occurs in one step)
R R C C
R R
C C "cis" alkenes form "cis" cyclopropane rings H H
H H
"trans" alkenes form "trans" cyclopropane rings
Example Reactions (Simmons-Smith reaction)

syn addition
CH2I2 / Zn(Cu) CH2
enantiomers
R and S
CH2
syn addition
CH2I2 / Zn(Cu)
enantiomers
RR and SS
CH2 syn addition

CH2I2 / Zn(Cu)
meso
RS and SR
syn addition
CH2
CH2I2 / Zn(Cu)
meso
RS and SR
CH2 syn addition
CH2I2 / Zn(Cu)
achiral
syn addition
CH2I2 / Zn(Cu) CH2
S S diastereomers
CH3 SSR and SRS
r. Alkenes with meta chloroperbenzoic acid (mCPBA). Synthesis of epoxides.

mCPBA (peroxyacid) has two electron buffered solution
poor oxygen atoms in the peroxide bond, prevents acid from
and the meta-Cl makes them even more reacting with epoxide
electron poor by its inductive effect.
O O
Cl 5 atoms Cl H
O O
View this complicated group
H O
of arrows as two different O one step
groupings in the transition 3 atoms concerted
state, one of five atoms and reaction C C
one of three atoms. It might R R
be easier to think about this way. R R
H H
C C The reaction can occur from either
the top face or the bottom face.
The alkene is electron rich. H H
costs (bond energy in kcal/mole) gains (bond energy in kcal/mole)

changes C=O (even trade) = -176
C=O (even trade) = +176 in energy
O-H (even trade) = + 110 O-H (even trade) = - 110
O-O (very weak) = +45 C-O (very weak) = -90
C=C (weak pi bond) = +64 C-O (very weak) = -90
ring strain of an epoxide Total = - 466
H = -44 kcal/mole
is also a cost = + 27 exothermic, even with ring strain
Total = + 422
Example Reactions (mCPBA)

Ar H O syn addition
(mCPBA) enantiomers
O O R and S
O
O
syn addition
Ar H
(mCPBA) O O enantiomers
RR and SS
O O
syn addition
Ar H
meso
(mCPBA) O O RS and SR
O
syn addition
Ar H
O
meso
(mCPBA) O O RS and SR
O
O syn addition
Ar H
(mCPBA) O O achiral
O
syn addition
Ar H
O
(mCPBA) O O diastereomers
S S SSR and SRS
s. Alkenes with OsO4 or KMnO4. “Syn” synthesis of vicinal diols.

KMnO4 and OsO4 change in oxidation state...?
are electron poor each carbon goes from -1 to 0 (2 electrons lost)
manganese goes from +7 to +5 (2 electrons gained)
O O K
Mn O O O O O O O H
O O Mn O
Mn Mn
O O O O H H
R KMnO4 O O H
R
C C H2 O C C C C C C
R R R R R
HO R
H H H H H H
H H
The stereochemistry is Use analogies with hydroxide
The alkene is electron rich set at this point as "syn" hydrolysis of esters and imides
addition presented earlier.
O O
O H O O
H H Mn O H
H H O
O O Mn
O O H O O H
C C
R R C C
R R C C
H H H R R
H
OsO4 has a similar mechanism. H H
Very expensive OsO4 can be continually reoxidized with an inexpensive amine oxide (like morpholine N-
oxide)
O O O
O resonance
O N O N + O Os O
Os O Os O
O O
O O
reduced OsO3 morpholine osmium tetroxide
amine oxide
(Os = +8)
(N = -1) (Os = +6) (N = -3)
Example Reactions
OsO4
or OH syn addition
KMnO4 OH
achiral
OH
OsO4
or syn addition
KMnO4 CH3
S S diastereomers
OH SSR and SRS
t. Alkenes with 1. O3 / -78oC 2. CH3SCH3 or Zn. Synthesis of aldehydes or ketones.

Ozone is an electron
poor oxidzing reagent.
O O O
O
O O O O
O
-78oC C2
C1 C2 -78oC C1
R R H R
R R R R
Cyclic five atom Peroxide
transition state R H rotate
bond
C1 C2 with six electron ruptures resonance 180o
movement. Molozonide is highly (shown).
R H unstable, even at -78oC O
and rearranges to a more O H R
Simple alkenes are electron rich. C2
stable ozonide with only
one peroxide bond. C1
R R O
Rejoins with only

one peroxide bond
S (use polarities).
O O O O
resonance H3C CH3 O O
R
S S C1 C2 R
H3 C CH3 H3 C CH3 R R H R C1 C2
O H
dimethylsulfoxide ketone aldehyde R
(DMSO) ozonide
o
The C=C is completely cleaved at -78 C. The second step decides
what will happen to the ozonide. In this example, it is reduced by
DMS to two carbonyl compounds, (an aldehyde and a ketone).
Example Reactions
O
1. O3 / -78oC
2. CH3SCH3 CH O
H3 C H2 C
O
1. O3 / -78oC CH3
2. CH3SCH3 CH HC
H3C
O
O
1. O3 / -78 C o CH3
2. CH3SCH3 CH HC
H3 C
O
O
1. O3 / -78oC C
H
2. CH3SCH3 H
C
O
1. O3 / -78oC
2. CH3SCH3 O
O
H2 C
O
o
1. O3 / -78 C C
H
2. CH3SCH3
CH3
S S
O
u. Alkenes with 1. O3 / -78oC 2. NaBH4. Synthesis of alcohols.

O
O O BH3
H BH3 ketone aldehyde
O O
o
R O O
-78 C R b. NaBH4 workup
R R C1 C2
H BH4-- is electron C1 C2
C1 C2 several R O
steps rich, the ozonide R R H R
ozonide is electron poor
R H
H BH3 H BH3
H H
O O
H O H O O
R C R H C R
H R C R H C R
H H final workup
The ketone becomes The aldehyde becomes (neutralization) H H
a secondary alcohol. a primary alcohol.
Example Reactions
OH
1. O3 / -78oC
OH
2. NaBH4
H3C
OH
o
1. O3 / -78 C
2. NaBH4
OH
OH
1. O3 / -78oC
2. NaBH4
OH
1. O3 / -78oC
2. NaBH4 OH
OH
H3 C
OH
diastereomers
1. O3 / -78oC (SR and SS)
2. NaBH4
CH3
S S
OH
v. Alkenes with 1. O3 / -78oC 2. H2O2 / HO--. Synthesis of carboxylic acids or ketones.

O
O O
O H ketone
O O peroxide intermediate
o
R O OH
-78 C R b. NaBH4 workup O O
R R C1 C2
H BH4-- is electron C1
C1 C2 several R O C2
steps rich, the ozonide R R
R H
ozonide is electron poor
R H rearrangement
of peroxide
(hydride shift)
O H O H
O
H O H basic
O O H
conditions C2
H H
C2 C2 R O
H
R O final workup R O
(neutralization)
carboxylic acid
Example Reactions
O HO O
1. O3 / -78oC C
2. H2O2 / HO C
H3C OH OH
O
1. O3 / -78oC
2. H2O2 / HO C
H3C OH
O
1. O3 / -78oC
C
2. H2O2 / HO
H3 C OH
CO2H
1. O3 / -78oC
2. H2O2 / HO CO2H
HO O
1. O3 / -78oC
O C
2. H2O2 / HO
OH
CO2H
1. O3 / -78oC
2. H2O2 / HO CH3
S S
O
w. Alkenes with Pd / H2. Synthesis of “alkane” from “alkene” (hydrogenation). Simplistic mechanism:
Hydride transfer
also bonds carbon
H H H to the metal atom. H
C C
M M M M C
H C C C
H H H
metal HOMO metal HOMO metal hydride
metal hydride
H2 LUMO  bond LUMO sigma bond complex
pi bond complex
Hydride transfer
releases an alkane
and regenerates
the metal catalyst.
H
C
H C
M
adds H2.
Neutral metal atom can begin Syn (cis) addition of two hydrogens
the process over = catalytic. to the pi bond. Generally H 2 adds
from the less sterically hindered face
(i.e. the H2 adds to the more open face).
Example reactions
syn addition
Pd / H2
achiral
syn addition
Pd / H2
achiral
syn addition
Pd / H2
achiral
syn addition
Pd / H2
achiral
syn addition
Pd / H2
achiral
syn addition
Pd / H2
diastereomers
S SR and SS
S
x. Alkenes with Pd / D2. Same hydrogenation reactions with deuterium from “alkene” (hydrogenation
w/”D” = deuterium).
* = chiral center D
syn addition
Pd / D2 S D
* R/S
D
syn addition
R
Pd / D2 *
*
R RR and SS
(enantiomers)
D
D
syn addition
R D
Pd / D2
*
* S RS and SR
(meso,achiral)
R D
syn addition
Pd / D2 *
* RS and SR
(meso,achiral)
S D
D D syn addition
Pd / D2
achiral
R D
syn addition
Pd / D2 *
D
S * * diastereomers
S SSR and SRS
S
y. Alkynes with aqueous sulfuric acid (plus some Hg+2 catalyst). Synthesis via enols (Markovnikov addition).
H2SO4 / H2O O
Markovnikov addition
= H3O+ (Hg+2) (enol tautomerization
to keto)
O
H2SO4 / H2O Markovnikov addition
= H3O+ (Hg+2) (enol tautomerization
to keto)
H2SO4 / H2O O
= H3O+ (Hg+2)
O
H2SO4 / H2O
= H3O+ (Hg+2)
Markovnikov addition
(enol tautomerization
to keto)
y. HX addition to alkynes. Markovnikov addition.
H Br Br
(or HCl or HI) Markovnikov
addition
Br
H Br
Markovnikov
(or HCl or HI) addition
H Br Br
(or HCl or HI)
Br
Br
H Br
(or HCl or HI)
Markovnikov
addition
z. Bromination (or chlorination) of alkynes. Bridging bromonium ion.
Br2 Br
or
Cl2 anti addition
Br
Br
Br2
or anti addition
Cl2
Br
Br
Br2
or anti addition
Cl2
Br
Br
Br2
or
Cl2 anti addition
Br
aa. 1. Hydroboration 2. oxidation of alkynes (anti-Markovnikov addition makes aldehydes or ketones via enolate).
O
1. HBR2
2. H2O2 / HO anti Markovnikov
addition
H
O
1. HBR2 anti Markovnikov
2. H2O2 / HO addition
O
1. HBR2
2. H2O2 / HO
O
1. HBR2
2. H2O2 / HO anti Markovnikov
O addition
bb. Catalytic hydrogenation reduces triple bond to “alkane”.
Pd / H2
Pd / H2
Pd / H2
Pd / H2
cc. Catalytic hydrogenation with quinoline “poison” of Pd catalyst reduces triple bond to Z alkene (syn addition).
Pd / H2
quinoline
(Lindlar's Cat.)
Pd / H2
quinoline
(Lindlar's Cat.)
Pd / H2
quinoline
(Lindlar's Cat.)
Pd / H2
quinoline
(Lindlar's Cat.)
dd. Sodium metal + liquid ammonia reduction of triple bond to E alkenes.
Na / NH3
(liq - =33oC)
Na / NH3
(liq - =33oC)
Na / NH3
(liq - =33oC)
Na / NH3
(liq - =33oC)
ee. Zipper reaction moves triple bond to terminal position where it can be removed to form sp carbanion nucleophile.
1. NaNR2
2. WK
Zipper reaction
1. NaNR2
2. WK
Zipper reaction
1. NaNR2
2. WK
Zipper reaction
1. NaNR2
2. WK
Zipper reaction
ff. Formation of conjugate base + addition of aldehyde electrophile forms propargyl alcohol.
1. NaNR2 OH
2. O
1. NaNR2 OH
2. O
1. NaNR2 OH
2. O
1. NaNR2
2. O
H
OH
gg. Formation of conjugate base + addition of ketone electrophile forms propargyl alcohol.
1. NaNR2
2.
O
OH
1. NaNR2
2.
O
OH
1. NaNR2
2.
O
OH
1. NaNR2
2. OH
O
hh. Formation of conjugate base + addition of methyl or primary RX electrophile forms a longer alkyne.
1. NaNR2
2.
Br
1. NaNR2
2.
Br
1. NaNR2
2.
Br
1. NaNR2
2.
Br
ii. Formation of conjugate base + addition of secondary electrophile reacts in a nonproductive E2 reaction.
1. NaNR2
2. Br
E2 reaction
1. NaNR2
2. Br
E2 reaction
1. NaNR2
2. Br
E2 reaction
1. NaNR2
2. Br
E2 reaction
jj. Use zipper reaction to move alkyne through a linear chain to the end position. Work up 4 ways: a. with
mild acid to generate the terminal alkyne, b. with an MeX or primary RCH2X to make a longer alkyne, c. with
an aldehyde or ketone compound (C=O) or d. with an epoxide.
1. excess NaNR2
2. workup
1. excess NaNR2
2. Br
Ph
Ph Ph = phenyl
1. excess NaNR2
2. H2C O OH
3. workup
1. excess NaNR2
2. O OH
Ph
Ph Ph = phenyl 3. workup
kk. Formation of conjugate base + addition of epoxide electrophile forms an alkynyl alcohol via SN2 reaction.
1. NaNR2
2. O R
R OH
1. NaNR2 OH
2. O
1. NaNR2
OH
2. O
1. NaNR2
2. O
R OH
R
ll. Epoxides with terminal acetylides (followed by workup = neutralization).
Na HO
O
R
achiral
2. WK R
O Na HO R
R chiral
R
2. WK R
Na R
O
OH
R
achiral
2. WK
R
R
Na
S
O
R and SRR
S S
2. WK
S S OH diastereomers
mm. Epoxides with lithium diisopropyl amide (LDA, followed by workup = neutralization).
1. Li R OH
R N
R R
O lithium diisopropylamide (LDA)
2. WK S
S enantiomers
1. Li
O N
R R achiral
lithium diisopropylamide (LDA) OH
R
2. WK
1. Li
O N OH
R R
lithium diisopropylamide (LDA) achiral
2. WK
not stereoismers R OH
R 1. Li
N
O R R
lithium diisopropylamide (LDA)
S 2. WK S
S
S S OH
nn. Aldehydes and ketones with terminal acetylides.
OH
O Na
1. R
2. WK
H enantiomers (R and S)
R
O Na enantiomers (R and S) R
1. R HO
2. WK
O OH R
Na
1. R
2. WK
achiral diastereomers
O OH
Na
1. R R
2. WK
enantiomers (R and S)
oo. Aldehydes and ketones with secondary amines (enamine synthesis, alkylation, hydrolysis).
H
TsOH (-H2O)
O N
N
o
2 amines E & Z possible
H
H
H
O
TsOH (-H2O)
N
N
E & Z possible
o
2 amines
H
O TsOH (-H2O)
N N
2o amines
achiral S R also possible
H
O TsOH (-H2O)
N N
2o amines

Organic Reactions Summary Alkenes, Alkynes and Variations For Use As A Study Guide Beauchamp

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Organic Reactions Summary Alkenes, Alkynes and Variations For Use As A Study Guide Beauchamp

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Alkenes, Alkynes & Variations Beauchamp 1

Organic Reactions Summary

For Use as a Study Guide

Making alkenes and alkynes

NaCC-R E2 > SN2

Schlosser Modification of the Wittig reaction to make E alkenes

Possible mechanism – with mechanism details

Reactions of alkenes, alkynes and conjugated variations

1. initiation (two steps)

b. RBr from alkenes (anti-Markovnikov addition of HBr using borane chemistry):

() or (dl) enantiomers

The large mercury atom with extra d electron densitiy bridges

The initial adduct is a stable, organomercury compound, O O

H O The Hg bridge helps to

1. HgX2 / H2O enantiomers

1. HgX2 / H2O diastereomers

The large mercury atom with extra d electron densitiy bridges

The initial adduct is a stable, organomercury compound, O O

H3C O The Hg bridge helps to

1. HgX2 / CH3OH enantiomers

g. Electrophilic addition of HCl, HBr, HI to alkenes = Markovnikov addition, synthesis of RX compounds

only shows regioselectivity Markovnikov additioni

shows possible rearrangements Br

h. Electrophilic addition of HCl, HBr, HI to alkynes = Markovnikov addition, synthesis of RX compounds,

shows regioselectivity Markovnikov additioni

kinetic product thermodynamic product

j. Alkenes with Br2 or Cl2. Synthesis of vicinal dihalide (anti addition).

bromine is a red orange liquid (dl) mixture

chlorine is a green gas,

HC CH CH2 H2C H2C Br

k. Alkenes with Br2/H2O or Cl2/H2O. Synthesis of bromohydrin or chlorohydrin (anti + Markovnikov

Br2 / H2O OH anti + Markovnikov

l. Alkenes with Br2/ROH or Cl2/ROH. Synthesis of bromo or chloro “ethers”.

Br H3C (dl) mixture H3 C

H3C (dl) mixture H3 C

m. Alkenes with 1. BH3 2. H2O2/HO--. Hydroboration/oxidation = anti-Markovnikov alcohols.

1. BH3 1. syn addition

n. Alkenes with 1. BH3 2. Br2/CH3O--. Hydroboration/bromination = anti-Markovnikov R-Br.

1. BH3 1. syn addition

1. BH3 1. syn addition

o. Alkynes with 1. HBR2 2. H2O2/HO--. Hydroboration/oxidation = anti-Markovnikov aldehydes.

p. Alkenes with CHCl3 / RO-- or CHBr3 / RO--. Carbene synthesis of dihalocyclopropanes.

"trans" alkenes form "trans" cyclopropane rings

q. Alkenes with CH2I2 / Zn (Simmons-Smith Rxn). Carbenoid synthesis of cyclopropanes.

CBr2 syn addition

CCl2 syn addition

The first pair of dots represents

Example Reactions (Simmons-Smith reaction)

CH2 syn addition

CH2 syn addition

r. Alkenes with meta chloroperbenzoic acid (mCPBA). Synthesis of epoxides.

costs (bond energy in kcal/mole) gains (bond energy in kcal/mole)

Example Reactions (mCPBA)

s. Alkenes with OsO4 or KMnO4. “Syn” synthesis of vicinal diols.

t. Alkenes with 1. O3 / -78oC 2. CH3SCH3 or Zn. Synthesis of aldehydes or ketones.

Rejoins with only

u. Alkenes with 1. O3 / -78oC 2. NaBH4. Synthesis of alcohols.

v. Alkenes with 1. O3 / -78oC 2. H2O2 / HO--. Synthesis of carboxylic acids or ketones.

y. HX addition to alkynes. Markovnikov addition.

z. Bromination (or chlorination) of alkynes. Bridging bromonium ion.

bb. Catalytic hydrogenation reduces triple bond to “alkane”.

dd. Sodium metal + liquid ammonia reduction of triple bond to E alkenes.

ll. Epoxides with terminal acetylides (followed by workup = neutralization).